Dimethylformamide → 2-[3-Methoxy-4-[(4-methoxyphenyl)methoxy]phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane

HRID 603086ノート

反応式

HRID 603086 の反応式
[CH3:1][O:2][C:3]1[CH:8]=[C:7]([B:9]2[O:13][C:12]([CH3:15])([CH3:14])[C:11]([CH3:17])([CH3:16])[O:10]2)[CH:6]=[CH:5][C:4]=1[OH:18].CN(C=O)C.[H-].[Na+].[CH3:26][O:27][C:28]1[CH:35]=[CH:34][C:31]([CH2:32]Cl)=[CH:30][CH:29]=1>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.C(OCC)C>[CH3:1][O:2][C:3]1[CH:8]=[C:7]([B:9]2[O:10][C:11]([CH3:17])([CH3:16])[C:12]([CH3:14])([CH3:15])[O:13]2)[CH:6]=[CH:5][C:4]=1[O:18][CH2:32][C:31]1[CH:34]=[CH:35][C:28]([O:27][CH3:26])=[CH:29][CH:30]=1

参加物

7

反応物 4

HCID 6228DimethylformamideHCID 24758Sodium hydrideHCID 699934-Methyloxybenzyl chlorideHCID 27346502-Methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol

生成物 1

HCID 670612332-[3-Methoxy-4-[(4-methoxyphenyl)methoxy]phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane収率 100%

試薬・触媒・溶媒 2

HCID 67553Tetrabutylammonium Iodide触媒HCID 3283Diethyl Ether溶媒

実験手順

2-[3-Methoxy-4-(4-methoxy-benzyloxy)-phenyl]-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane was prepared as follows. To a flame-dried 50 ml round bottomed flask were added 2-methoxy-4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenol (1.00 g, 4.00 mmol) and anhydrous DMF (20 ml). Sodium hydride (251 mg, 6.29 mmol; 60% dispersion in mineral oil) was added in three portions, and the suspension was stirred under nitrogen for 30 minutes para-Methoxy benzyl chloride (655 μl, 3.62 mmol) and tetrabutyl ammonium iodide (10 mg, 0.03 mmol) were added, and the reaction mixture was stirred for an additional 16 hours. The reaction mixture was concentrated, then cooled in an ice-bath, and 50 ml of 1 M citric acid was added followed by 100 ml ethyl acetate. The layers were separated, and the aqueous phase was extracted three times with ethyl acetate. The combined organic fractions were washed with brine, dried (Na2SO4), filtered and concentrated to give a tan powder. Trituration with diethyl ether gave 1.34 g (91%) of 2-[3-Methoxy-4-(4-methoxy-benzyloxy)-phenyl]-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane as a tan powder. 1H-NMR (CDCl3) δ=7.35 (m, 2H), 7.29 (s, 1H), 7.26 (s, 1H), 6.89 (m, 3H), 5.11 (s, 2H), 3.91 (s, 3H), 3.80 (s, 3H), 1.33 (s, 12H); MS m/z: 393 [M+Na]+.

後処理

  1. custom2-[3-Methoxy-4-(4-methoxy-benzyloxy)-phenyl]-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane was prepared
  2. additionwere added
  3. concentrationThe reaction mixture was concentrated
  4. temperaturecooled in an ice-bath
  5. addition50 ml of 1 M citric acid was added
  6. customThe layers were separated
  7. extractionthe aqueous phase was extracted three times with ethyl acetate
  8. washThe combined organic fractions were washed with brine
  9. dry with materialdried (Na2SO4)
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customto give a tan powder

出典と根拠

ORDレコード
ord-99222d4bd45b40d5bcf192cd32418a3d
出典データセット
uspto-grants-2011_03
特許番号
US07906648B2

反応ノート

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